Azo dyes



Patented .Iuly 15, 1941 UNITED STTES AZO DYES Delaware No Drawing. Original application June 4, 1938,

Serial No. 211,798. Divided and this application June 12, 1940, Serial No. 340,122

9 Claims.

This application is a division of our copending application Serial Number 211,798, filed June 4, 1938, now Patent No. 2,228,415, issued Jan. 14,

This invention relates to new azodyes of the type whose properties are improved by aftertreatment with formaldehyde. The invention relates to the dyes both before and after such treatment.

It was long ago proposed to treat certain azo dyes on the fiber with formaldehyde to improve the properties thereof. Examples thereof are shown in U. S. Patents 1,150,656, 1,169,329, 1,090,379, 1,125,050, 1,087,430, and 1,082,925. Despite the existence in the art of such colors however the dye industry has gone more and more to the use of two bath processes in which the one intermediate is applied to the fiber in one bath and the other added in the second bath, or in which the intermediates are stabilized against each other in a paste and then reacted on the fiber, because such colors have properties superior to those which are possessed by the types of direct, formaldehyde-treated dyes of these references. It is, however, highly desirable to apply complete dyes directly provided the complete color has the requisite brilliance and fastness.

It is, accordingly, an object of this invention to prepare direct dyes of high quality and fastness when after-treated with formaldehyde.

The objects of the invention are accomplished, generally speaking, by azotizing a compound represented by the formula:

I l 2 l I H2N in which 13 is one of the group of radwhere m is a digit other than Zero and in which each R is one of the group consisting of hydrogen, alkyl, aryl, aralkyl, halogen, alkoxy, nitro,

sulfonic carboxylic, and ON; coupling the amtized compound to one ofthe following components: an amino-phenyl-pyrazolone; a l-amino-naphthalene represented by the formula:

in which each R, is one of the group consisting of hydrogen alkyl, and alkoxy, and the -I-I' a l-amino-naphthalene sulfonic acid represented by the formula:

NHz 3R 1 in which it is preferred that the nucleus shall contain only one sulfonic acid group. The compound so formed is azotized and coupled to a 1,3- dihydroXy-benzene of the formula:

(IDH

where Z is one of the following group: H,

alkyl, alkoXy, amino, SOsH, COOI-I, halogen, and

ON; dyeing appropriate material therewith and reacting the product on the material with form- The preferred end component is 1,3-dihydroxybenzene. The completed compounds have the type formula before the formaldehyde treatment:

in which X is the component first described in the preceding paragraph; Y is the component next described, and A is the compound last described in said paragraph, of which class resorcin is preferred.

Where a symbol such as 4R is used, it means that the indicated number of members of the group R appear as substituents in the nucleus. For example, it could mean three hydrogens and a methyl (both being in the group R); or two alkyls, a halogen, and a hydrogen; or any other razolone-3-carboxylic acid and 5000 parts of water. Add 106 parts of sodium carbonate. Stir until complete solution is obtained. The solution should be alkaline to Brilliant yellow paper. Add 265 parts of sodium carbonate and stir until dissolved. Ice the solution to 0 C.

Add the solution of the tetrazo slowly to the solution of 1- (3-amino-phenyl) -5-pyrazolone-3- carboxylic acid. Maintain a temperature of 05 C. There should be an excess of 1-(3'-aminophenyl)-5-pyrazolone-3-carboxylic acid. Maintain a temperature of 0-5 C. There should be an excess of 1-(3-aminophenyl) -5-pyrazolone- B-carboxylic acid as shown by spotting with 4,4- diamino 3,3 dimethoxy diphenyl tetrazo. There should be no test for the tetrazo by spotting with an alkaline solution of 1-amino-8- naphthol-3,6-disulfonic acid (H-acid). Stir the yellow-orange dye suspension for one hour. Heat the mixture to- -80 C. Salt 5% with sodium chloride and filter.

Stir the filter cake with 4000 parts of water until a smooth slurry is obtained. Ice to 10 C. Add parts of 100% hydrochloric acid as a 30% solution. Add 69 parts of 100% sodium nitrite as a 30% solution. Tetrazotize at 10-12" C. for one hour with a distinct excess nitrite.

Stir 132 parts of l,3-dihydroxy benzene and 2500 parts of water to complete solution. Ice to 0 C. and add 215 parts of sodium carbonate.

Add thetetrazo slowly to the alkaline solution of 1,3-dihydroxy benzene. There should be an excess 1,3-dihydroxy-benzene as shown by spotting with 4,4-diamino-3,3-dimethoxy-diphenyl tetrazo. Stir one hour after the addition of the tetrazo. Heat the suspension to 70-80 C. Salt slowly 10% with sodium chloride. Filter. Dry

at 8085 C. in an oven. The dry powder is red orange in appearance.

combination of members of that group. To have a small number of non-hydrogen substituents is in accordance with the better practice because of cost and complexity in manufacture. Where R appears in one ring of a naphthalene nucleus and R in the other, it is to be understood that each said symbol appears only in the indicated half of the nucleus. On the other hand, where a symbol is shown alone in a naphthalene nucleus, it may appear at any replaceable position.

The following examples illustrate but do not limit the invention:

EXAMPLE I The dye may be dyed on the fiber and aftertreated as follows:

Dissolve 0.2 gram ofthe product in 50 ml. water at 190-200 F., adding 0.4 gram of sodium carbonate to assist the solution. Dilute with stirring to a total volume of 500 ml. With Water at approximately F. Add 49 ml. of a 10% solution of Glaubers salt. Wet out a 10 gram piece of rayon with water, squeeze partially dry, and enter this into the dye bath. Raise the temperature of the dye bath to -190 F. in the course of fifteen minutes. Hold the dye bath at that temperature for one hour. Stir the dyeings at frequent intervals during this time. At the end of one hour remove the dyeing and rinse in cold water.

After-treatment in a fresh bath To 500 ml. of water at 130-140 F. add the this temperature for twenty minutes. Remove the dyeing, rinse, and dry.

After-treatment in the dye bath An alternative after-treating process, which is the preferred procedure because of its economy and ease of application, is carried out as'follows:

At the end of the dyeing period add to the dye bath 10 ml.- of 10% formaldehyde as in the preceding example at bath temperature. Remove the dyeings after twenty minutes. Rinse and dry.

A dyeing with a bright orange shade is obtained which shows excellent fastness to washing and yields white discharges.

It is understood that We are not limiting'ourselves to the exact conditions of the above operations which may be varied within reasonable limits as will be readily recognized by one skilled in the art without essentially altering the dyeing and fastness properties of the subject product.

EXAMPLE II Slurry 144 parts of 3- (4' -amino-benzoylamirio)-1-amino benzene and 4000 parts of Water. Add 91 parts of 100% hydrochloric acid as a 30% solution and warm to 35-40 C. for complete solution. Ice to C. Add 69 parts of 100% sodium nitrite as a 30% solution. Tetrazotize at 05 C. for one-half hour with a faint excess nitrite. The soluble tetrazo should be distinctly acid to Congo red paper.

Slurry 2 30 parts of 1-(3-=amino -phenyl)-5- pyrazolone-ii-carboxylic acid and, 5000 parts of water. Add 106 parts of sodium carbon-ate. Stir until complete solution is obtained. The solution should be alkaline to Brilliant yellow paper. Add 265 parts of sodium carbonate and stir until dissolved. Ice the solution to 0 C.

Add the solution of the tetra'zo slowly to the alkaline solution of the 1-(3'-amino-phenyl) pyrazol-one-B-carboxylic acid. Maintain a temperature of 0-5" C. There should be an excess of; 1- (3' -amino-phenyl) -5-pyrazolone-3-carboxylic acid as shown by spotting with 4,4'-diamino- 3,3-;dimethoxy-diphenyl tetrazo. There should be no test for tetraz-o by spotting with. an alkaline solution of 1--amino-8-naphthol-3,6-disulfonic acid (I-I-acid). Stir the yell-ow suspension for one hour. Heat the mixture to '7080 C. Salt 5% with sodium chloride and filter.

Stir the filter cake with 4000 parts of water until a smooth slurry is obtained. Ice to C. Add 110 parts of 100% hydrochloric acid as a solution. Add 69 parts of 100% sodium nitrite as a 30% solution. Tetrazotize at 10-12 C. for one hour with strong excess nitrite.

Stir 132 parts of l,3-dihydroxybenzene and.

The product may be dyed and after-treated in amanner analogous to that used in Example I. A,dyeing with a bright gold shade is ob,- tained which shows excellent fastness to washing and yields white discharges.

' EXAMPLE III Slurry '187 parts of 4,4-'diainino-stilberie-Z,2 disulf-onic acid and 4000 parts of water. Add 42 parts of sodium hydroxide andstir until complete solution is obtained. The solution should be slightly alkaline to Brilliant yellow paper. Ice to 10 C. Add 1 28 parts of 100% hydrochloric acid as a 30% solution. Add 69 parts of 100% sodium'nitrite as a 30% solution. Tetrazotize at 10-1 2C.f-or forty-five minutes with a slight excess nitrite. Remove the excess nitrite just before coupling. w

Slurry 234 parts of l-amino-naphthalene-G- sulfonic acid and 4000 parts of Water. Add

parts of sodium carbonate or a sufiicient quan tity to obtain a complete solution which is faint- 1y alkaline to Brilliant yellow paper. After stirring to insure complete solution a suificient quantity of acetic acid is added to make the solution faintly acid to litmus paper. I

Ice the tetrazo to 0 G. Add 135 parts of hydrated sodium acetate. Add the neutral solution of l-amino-naphthalene-6-sulfonic acid. The suspension should be neutral to Congo red paper and acid to litmus paper. Stir fifteen to twenty hours to insure complete coupling allowingthe. temperature to rise to 2030 C. There should be a distinct test for l-amino-naphthalene-(i-sulfonic acid. Heat. the suspension to 70-80? C. Salt 5% with sodium chloride. Filter.

Slurry the filter cake and 3000 parts of wa-- ter. Ice to 12-15 C. .Add 110 parts of 100% hydrochloric acid as a 30% solution. Add 69 parts of 100% sodium nitrite as a 30% solution.

Tetr-azotize for one and one-half hours with. a

' distinct excess nitrite at 1 5-20 C.

' in 2000 parts of water.

Dissolve 132 parts of l,'3-dihydroxy" benzene parts of sodium carbonate.

Add the tetrazo slowly to the alkalinesolution of 1,3-dihydroxy-benzene. Stir one hour after the addition. There should be a distinct excess of 1.3-dihydroxy benzene and the suspension should be alkaline to Brilliant yellow paper. Heat to 70450 C. Salt 10% with sodium chloride. Filter. Dry at 85 C. in an oven. The dry powder is a blue black in appearance and when dyed and after-treated with formaldehyde gives a blue' violet shade. This: product 'sho ws,ex-

Ice to 0 C. Add. 215

oellent washing fastness and good discharge with 1500 parts of water. Add 55 parts of 100% properties. The probable formula is: hydrochloric acid as a 30% solution. Stir until N=N- N=NQC=C N=N- N=NQOH lilo-U011 SO3Na SOaNa I 8 H v oiNs 803N8- EXAMPLE IV dissolved. Ice to C. Add 42 parts of 100% sodium nitrite. Tetrazotize for one-half hour Slurry 114 parts of 4-(4 -amino-benzoy1)- witha'snght excess nitrite.

amino-l-amino-benzene with 4000 parts of water. Add 91 parts oi 100% hydrochloric acid as a 30% F parts 0f -f solution. Warm to 35-40 C. for complete solufomc a c1d and 2000 parts watel- Add 65 poarts tion. Ice to 0 0. Add 69 parts of 100% sodium sOdlum carbmate to dlssolve- Ice to 0 Add 130 parts of sodium carbonate. mtrite as a 30% solution. Tetrazotize at 0-5 0. for 30 minutes with Slight excess nitrite Add the tetrazo slowly to the coupling solut1on.

Maintain an excess of 2-amino-8-naphthol-6-sulparts of 1 ammo 5 naphthol 7 fonic acid and sodium carbonate alkalinity. Stir sulfonic acid and 4000 parts of water. Add 106 20 one hour Heat to 70 80 C salt 7 parts of sodium carbonate and stir for complete 0 W1 l k sodium chloride, stir and filter. 235 3 5 3 52;? g gg 3 223 32 Slurry the filter cake and 3000 parts of water parts of sodium carbonate to a smooth slurry Ice to 540 Add 66 parts a f 100% hydrochloric acid as a solution. Add the tetrazo slowly to the coupling solution. o O Maintain a temperature of and a strong Tetrazotize at 5-10 C. for one hour with strong xcess nitrite alkalinity on Brilliant yellow paper. Stir one 6 hour after the addition of the tetrazo. There Dlssolve 82 parts of j benzene m Should be an excess of 1 amino 5 naphtho1 7 1500 parts of water. Ice to 0 0. Add 150 parts sulfonic acid. Heat the mixture to '70-80 c. 30 g g? i 1 Salt slowly 5% with sodium chloride and filter. d e e razo 5 0w y to alkaline solutlon Slurry the filter cake and 4000 parts of water q benzene; m The until wen broken up Ice to C. Add 110 parts suspension should be alkaline to Brilliant yellow of 100% hydrochloric acid as a 30% solution. 133113.913 tto 70-00 C. Salt slowly 10% with Add 69 parts of 100% sodium nitrite as a 30% sodlum ch1r1dei Dry at m an solution. Tetrazotize at 10-15 C. for one'hour Oven- The product 15 a black p wder which vith a excess nitrite when and after-treated as in I Dissolve 132 parts of 1,3-dihydroxyl benzene in iv s e p rown h d w th e l en W hi 2500 parts of water. Ice to 0 C. Add 215 parts fastness and good discharge properties. of sodium carbonate. 7 40 The probable formula is:

OH R 7 HO- -SOaNa Naois- $0 I OH Add the tetrazo slowly to the alkaline 1,3-dihy- EXAMPLE VI droxy benzene solution. Maintain a temperature of 0-5 0., a distinct excess of 1,3-dih drox ben- Slurry 90 pa ts f -d -a y Zena and Brilliant yellow alkalimty st one amino) -ethane and 2000 parts of water. Add hour. Salt slowly 5% with sodium chloride. 55 Parts yd oc oric acid as a 30% solu- Filter. Dry at 80-85 C. in an oven. The dry tion. Add 42 parts of 100% sodium nitrite as a. powder is a bluemmwn in appearance and when 30% solution. Tetrazotize at 0-5 C. for one-half dyed and after-treated as in Example I gives a hour with a slight excess nitrite.

maroon shade showing excellent washing and Slurry 148 parts of 1-amino-5-naphthol-7-suldischarge properties. fonic acid with 2500 parts of water. Add parts The probable formula is: of sodium carbonate. Stir to complete solution.

I lYI=N-QOH 0 N N 0 s HO. HO S a a g I? B a H A H A H v 7 EXAMPLE V Ice to 0 0. Add 127 parts of sodium carbonate.

Slurry 73 parts of di-(4-amino-phenyl) urea Add e tetrozo lowly to the alkaline solution.

Stir one hour. The suspension should be alkaline 2500 parts of water. Ice-to C. Add 1215 parts to Brilliant yellow and there should be present of sodium carbonate.

an excess of 1-amino-5-naphthol-7-sulf0nic acid. Add the tetrazo slowly to the alkaline solution Heat to '7080 C. Salt 10% with sodiumchlo of the" 1,3-dihydroxy1benZene. Stir. one hour. ride. Filter. 5 There should be a distinct excess of 1,3-dihy- Slurry the filter cake with 3000 parts of water. droxy benzene and" the suspension should be al Ice to C. Add 66 parts of 100% hydrochloric kaline to Brilliant yellow; Heat to 60-70" C. acid as a 30% solution. Add 42 parts of 100% Salt 10% with sodium chloride. Filter. Dryi at sodium nitrite as a 30% solution. Tetrazotize at 80-85 C. in an oven. The dry brow p wder 10-l5 C. for one hour with strong excess nitrite. 10 W dy d after-treated as in pl I Dissolve 80 parts of 1,3-dihydroxy-benzene in gives a yellow Bordeaux shade with excellent 2000 parts of water. Ice to 0 G. Add. 150 parts washing fastness and good, discharge properties. ofsodium carbonate. The probable formulais:

HO OH H 'OH" Add the tetrazo slowly to thealkaline solution EXAMPLE VIII of 1,3-dihydroxy benzene. Stir one hour. There should be an excess of 1,3-dihydroxy benzene and the suspension should be alkaline to Brilliant yellow paper. Heat to 60-70 C. Salt slowly 10% with sodium chloride. Filter. Dry at 8085 C. in an oven. The brown powder when dyed and after-treated with formaldehyde yields a red brown shade with excellent washing fastness and good discharge properties.

Slurry 140 parts of 4,4-diamino-diphenylamine-Z-sulfonic acid with 4000 parts of water. Add 91 parts of 100% hydrochloric acid as a solution. Filter if not completely dissolved. 7 Ice 2. 30% solution. Tetrazotize at 0-5 with a. slight excess of nitrite for 20-30 minutes.

ionic acid and 5000 parts ofwater. Add 106 30 to 0 0. Add 69 parts of 100% sodium nitriteas Slurry 2'50 parts of 2-amino-8=naphthol -6-sul- The probable formula is: parts of sodium carbonate; Stir until dissolved.-

OH H it a N=N CNCHzGHiNHC 3-N=N s oiNa NaOaS N: N=III on on EXAMPLE VII Ice to 0C. Add parts of sodium carbonate.

Add the tetrazo slowly to the alkaline coupling Slurry 121 parts of di-(3-amino-phenyl) -urea solution. Stir one hour after the addition of the with 4000 parts of water. Add 91 parts of 100% tetrazo. The suspension should be strongly al.- hydrochloric acid as a 30% solution. Stir to kaline to Brilliant yellow and should show a complete solution. Ice to 0 C. Add 69 parts of 5 distinct excess of 2-amino-S-naphthol-G-sulfonic 100% sodium nitrite as a 30% solution. Tetraacid. Heat to 60-70 C. Salt 20-25% with so-- zotize at 0-5 C. for one-half hour with a slight dium chloride. Filter. excess nitrite. Stir the filter cake and 4000 parts of water Stir 251 parts of 2-amino-5-naphthol-7-su1- until a smooth slurry'is obtained. Ice to 5 C.

fonic acid and 5000 parts of water. Add 106 parts 69 Add 110 parts of 100% hydrochloric acid. Add

of sodium carbonate. Stir to complete solution. 69 parts of 100% sodium nitrite as a 30% solu-' Add 265 parts of sodium'carbcnate and ice to tion. Tetrazotize at 5-10 C. for one hour;-

o C. Dissolve 132 parts of 1,3-dihydroxy benzene in Add the tetrazo slowly to the alkaline coupling .2500 parts of water. Ice to 0C. Add 215 parts mixture. Stir one hour. The suspension should -5 of sodium carbonate.

be strongly alkaline to Brilliant yellow and there Add the tetrazo slowly to the alkaline solution should be a distinct excess of 2-amino-5-naphof 1,3-dihydroxy benzene. Stir one hour after the thol-T-sulfom'c acid. Heat to 6070 C. Salt addition. There should be a distinct excess of 10% with sodium chloride and filter. 1,3-dihydroxy benzene and the suspension should Stir the filter cake and 4000 parts of'water m be alkaline to Brilliant yellow. Heatto60-70" C. to a smooth slurry. Add 110 parts of 100% hy- Salt 15% with sodium chloride. Filter. Dry at drochloric acid as a 30% solution. Ice to 10 C. -85? C. in an oven. The dry black powder Add 69 parts of sodium nitrite as a 30% when dyed and after treated as in Example I solution. Tetrazotize for one hour at 10-15 C. gives a black shade with excellent washing fast- Dissolve 132 parts of 1,3-dihydroxy benzene in 7751-? ness. i

The probable formula is:

I OH

similar results are obtained by reversing the order of adding the reagents, that is by adding,"

the copper sulfate solution first, treating for twenty minutes and then adding the formaldehyde solution. After twenty minutes the dyeings are removed, rinsed and dried.

In the trade there is a demand for colors which are fast to washing, which will not stain attached undyed fibers, and which can be applied by a process more simple than the socalled diazo process. These dyes are an answer to this demand of the trade. They have washing fastness equal, and in many cases much suart for any specific example. perior, to, the so-called d1azo colors. This ad- TABLE Combination Shade 1,3-di(4'-amino-benzoyl-amino) benzene 2 (l-(3-an1ino-phenyl) -5-pyrazolone-3-carboxylic Yellow.

acid); :3 (1,3-dihydroxy benzeneh. 3-(4-an1ino-benzoyl-amino)-l-am1no-benzenc :3 (2-an1mo-8-naphth0l-6-sulfonic HCKDR Red brown.

(1,3-dihydroxy benzeueh. 4-(4-amino-benzoyl-amino)-3-methyl-1-am1no benzene 1-; (Lannno-5-naphthol-7-sulfon1c Maroon.

acid)z 3 (1,3-dihydroxy benzene. 4-(4;amino-benzoyl-amino)-3-methyl-l-amino-benzene 3 (2-am1no-8-napl1thyl-6-sulfonic Do.

ac1d)z (LS-dihydroxy benzeneh. 3-(4-am1uo-benzoyl-amino)-1-amino-benzene :i (Z-amlno-5-naphthol-7-sullome acid); Scarlet.

:1 (Lii-dlhydroxy benzeneh. 1,2-d1(4fl-ammo-benzoyl-amino) ethane (2-am1no-8-naphtl1o1-6-sulfon1c acid :I Red brown.

(1,3-d1hydroxy benzene)z. 1,3-di(4-am1no-benzoyI-amino)benzene-4-sulfon1c acid (1-(3'-am1no-phenyl)-3-methyl- Yellow.

5-pyrazolone): I; (1,3-dihydroxy-benzene) 2. 4-(4-amino-benzoyl-amino)-3-chloro-l-a nmo-benzenc (1-(3-am1no-pheny1)-5-pyraz- Orange.

olone-3-carboxylic acid); 3 (l,3-d1hydroxy benzene) z. 4-(4'-ami.no-benzoyl-amino)-2-methyl-5-methoxy-l-am1no benzene 3 (2-am1no-5-napth- Maroon.

tho1-7-sulfonic acid); 1-, (1,3-dihydroxy benzene) z. 4-(4-amino-benzoy1-amino)-2-methyl-E-methoxy-l-amlno benzene :l (l-(3-amino- Scarlet.

phenyl)-5-pyrazolone'3-carboxylic acid): (1,3-d1hydrqxy benzene): Di)(4-amin)o-phenyl)urea :1 (l-amino-5-naphthol 7-sulion1c 801d): :2, (1,3-dihydroxy Red brown.

enzene z. D%)(3-amin)o-phenyl)urea :3 (2-amino-8-naphthol-6-sulfonic acid)z T, (1,3-dihydroxy Do.

enzene 2. Di(4-amino-phenyl)thio-urea I, (2-amino-8-naphthol-fi-sulfonic acid): :3, (1,3-dihy- Brown.

droxy benzene) z. DiS-aminf-phenybureaj(1-ammo-5-naphthol-7-sulfomc acid): 2 (1,3-d1hydroxy Red.

enzene 2. 4,4-diamino-diphenyl-amine 3 (Z-amino-B-naphthol-(i-sulfonic acidh l? (1,3-dihy- Black.

droxy benzene. 4,4'-diamino-diphenyl-am1ne-2-sulfon1c acid :3, (1-ammo-2-methoxy-naphthalene-fi-sul- Blue.

ionic acid); I; (1,3-dihydroxy-benzeneh. 4,4-diamino-stilbene-2,2-disulfomc acid :2, (1-am1no-3-methyl-benzene): :3 (13- Red brown.

dihydroxy benzene. w 4,4-diamino43,3-din:etliylhyphenyl-methane'1,- (1-(3'-am1no-phenyl)-5-pyrazolone-3-car- Orange.

boxylic acid); :1 (1,3-d1hydroxy-benzene)z. 3-(4-amino-benzoyl-amino)lamina-benzene 2 (1-(3-ammo-phenyl)-5-pyrazolone-8- Yellow.

carboxylic acid)z 2 (l-methyl-2,4,6-tr1hydroxy-benzene)z. 4-(4-amino-benzoyl-amino)-l-amino-benzene 2 (1-ammo-5-napl1tl1ol-7-sulfonic acid): Maroon.

:3 (1,3-dihydroxy-5-rnethoxy benzene. 3-(4-amino-benzoyl-amino)-1-an1inc-benzene (1;(3-am1no-phenyl)-5-pyrazolone-3- Yellow. w carboxylic acid)2 3 (1,B-dihydroxy-benzene-5-sulfonic ac1d)z.

are then removed, rinsed, and dried. Closely ,75.

vantage is very great from a standpoint of cost and ease of application. Equal or superior fastness can be obtained with less effort and less material expense on the part of the dyer. The azotization and development of the dyes on the fiber, as is required in the so-called diazo process, is unnecessary with these colors. There are three baths necessary in the so-called diazo process and only one is necessary in this process, al-

though as hereinbefore mentioned two baths can be used. In the case of diazo colors a shade change occurs when the development takes place on the fiber; This change is undesirable and makes it difficult for the dyer'to apply his shades accurately. These dyes present a solution to -HC=CH-, and

that problem because the formaldehyde aftertreatment produces practically no change in shade. These colors also have outstanding discharge properties, being in that respect at least Where m s 1 or 2 a d R is n or m f a r up equal, and in many instances far superior, to s s n f ydr n, a yl, a yl, y ,h 0-

the dyes of equivalent shades now on the market. g alkoXy, nitro, S lf n ylic, and CN.

The dyes can be applied to widely different The compounds 0f the pe materials, such as silk, wool, and leather, but

they are of particular importance in connection with the dyeing of cellulose and regenerated where A is resorcin, Y is an amino-naphtholcellulose. Some of the cellulose esters and ethers sulfonic acid and X is can also be dyed with highly satisfactory results.

R B. As many apparently widely diiierent embodil NH: ments of the invention may be made without de- Q l 5 parting from the spirit and scope thereof, it is to be understood that we do not limit ourselves to H2N the specific embodiments thereof except as deand B is e Of a group of radicals Consisting of fined in the appended claims. CONH, -NHCO We claim: R 1. The compounds of the class consisting of l NEGO- A Y X Y A -CONH I and A YeX- Y+A) formaldehyde CONH(CH2)mNHC'O-, NH, S, O, (CH2)m, in which A is resorcin, Y is an amino-naphtholand sulfonic acid and X is N l I NH2 D G where m is 1 or 2 and R. is one or more of a group consisting of hydrogen, alkyl, aryl, aralkyl, halo- HZN gen, alkoxy, nitro, sulfonic, carboxylic, and CN. and B is one of a group of radicals consisting of The Compound represented by the at 4. The compound represented by the formula:

OH OH 5. The compound represented by the formula:

on on w t N=NC CNO H2O HzNHQ-ON=N S O 3N8 N8 0 a S 1 q= N=lTT on 0H 1 o H o H -CONH, --NHCONH, NHCSNH-, 6. The formaldehyde complex of claim 3.

h 7. The formaldehyde complex of claim 2. R 8. The formaldehyde complex of claim 5.

l NHCO 9. The formaldehyde complex of claim 4. I CHILES E. SPARKS. STEWART C. HUSSEY.

' WILLIAM B. REYNOLDS. CONH(Cl-I2)mNl-ICO-, NH, S, O, (CHz)m, SWANIE S. ROSSANDER.

CERTIFICATE OF CORRECTION. Patent No. 2,2h9,53u. July 1 19in.

CHIIES E. SPARKS, ET AL.

It is hereby certified that error appears in the printed specification of the above numb ered patent requiring correction as follows: Page 2, sec- 0nd column, lines 9 to 11 inclusive, strike out thewords and period F'Mai ntain a temperature of 0-5 C. There should be an excess of l-(fi' aminophenyl)S-pyrazolone-B-carboxjlic acidf'; pagelt, first column, line 58, for 'Ydihydroxyl" read -dihydroxy-;'page 5, lines 11;. to 25 inclusive, in the formula, strike out the bond Connecting the center benzene rings; page 7, first column, line 21;, claim 1, before "A" at beginning of line" insert 7 a parenthesis; and that the said Letters Patent should'be read with this correction therein that the same may conform to the record of the case in the Patent Office.

Signed and sealed this 28th day of October, A. D. 1914.1."

Henry Van Arsdale, (Seal) Acting Conmissioner of Patents. 

